The role of the bulk scattering coefficient in extended near-infrared diffuse reflection (DR) spectrometry of materials with similar or identical absorption coefficients is demonstrated. Spectral differences that arise from intraclass variation in scattering coefficient strongly affect the ability to interpret certain spectral regions. Profound intraclass differences in both band intensities and band shapes in the DR spectra of both polyethylene and polystyrene samples are shown. The effects of saturation and Fresnel reflection are discussed. The enhancement of absorption by the matrix and other analytes in DR spectrometry through the addition of a liquid with an index of refraction which matches that of the matrix is also demonstrated.

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